Sulfuric and haloid acids



H. TOBLER. SULFURIC AND HALOID ACIDS. APPLICATION FILED IAN. 9,. I9I9.

Patented-Mm. 2, 1920.`

UNITED STATES PATENT oEEIoE. Y

AHENRI TOBLEB, OF HACKENSACK, NEW JERSEY, ASSIGNOB-'I'O AMERICAN BROMINE OOIMTANY, OF IAYWOOD, NEW JERSEY, A CORPORATION '0F NEW JERSEY.

sULrUBIc am mom acme.'

Specification ot Letters Patent.

Patented Mar. 2, 1920.

application mea January s, 1919. 'serial-1u. aman..

To all whom it may concern.'

Be it known that I, HENRI Tonnen residing at Hackensack, in the county of ergen, State of New Jersey, have invented certain new and useful Improvements vin Sulfuric and Haloid` Acids; and I do hereby declare the following to be a full, clear, and exact description of the invention, such as will enable others skilled in the art to which and hydrochloric acids in which every atom of sulfur employed is finally recoveredk 1n acid form, by dlrectly combining sulfur dioxid, chlorin and water.

Further objects of my invention reside in the provision of a process in which all materials entering the reaction areA recovered in the form of useful and desirable products and in the various combinations hereinafter described and claimed as will be a Earent'asl the invention is better undeistof y referv ence to the following speeificationwhen read 1n connection with the accompanying drawing diagrammatically illustrating an apparatus adapted for use in carrying out my 1nvention. v v

TheI production of sulfuric and hydrochloric acids have -previously' been mdcendently accomplished by distinct p having no relation otherthan that sulfuric acid, previously produced, is employed inthe manufacture ofh drocbloric acid.

Sulfuric acid is p uced by bringing sulfur dioxid into contact vwith nitren. oxld and water vapor in what is comme ycall the chamber processand also Aby bringing sulfur dioxidy into contact with heated catalytic nts in the so-called contact rocess.v ydrochloric acid is produ by heatin common salt with acld 1nA a hydrochloric acid evolved in water saturated solution is and continuously without until ,of materialnormally employed 1 n't epro- I The production of acid may be lndicated by equations as follows and the production of hydrochloric acid by the following equation .ployed in the hydrochloric acid process is destroyed and appears'in the form of sodium sulfate, a relatively valueless product diiicultly disposable and entirely undesirable from any standpoint. The only useful prod- 4uct resulting from the two processes 1s the hydrochloric acid recovered.

I have 't discovered that sulfur dioxid, chlorin and water may be directly and con- 'currently combined to produce sulfuric and ,hydrochloric acids in accordance with thev following equation-:-

' SO,+2C1+2II,O=H,SO,+2HC1 which indicates the.ultimate combination,

.although it is of course to be understood that var iousminor and more or less obscure reactions occur during the combination which 1t 1s not necessary to illustrate in detail in order that my invention may be understood.

I obtain the sulfur dioxid b burning sulfur or roasting pyrites in o inary burners such as is commonl used in the manufacture of sulfuric acid. e chlorin is obtained by decomposing common salt or sodium chlond in an electrolytic cell of the diaphragm ormercury type and accordance with the well understood `principleas indicated by the following equation 2NaCl-I-electricity-l-2H O:

2c1+2NaoH+H, As will be readily apparent by reference to the equation illustrating the direct combination of sulfur dioxid and chlorin to produce .sulfuric and 'lydrochloric acids in connectionwith the o statement as to the source of the sul dloxid and chlorin, I am able torobtain from the same uantity i duction of hydrochloric acid alone, to-wit,

one atom of sulfur and two molecules of common salt or sodium chlorid, three important chemicals which are the sole products of the reactions involved. These products are one molecule of sulfuric acid, two molecules of hydrochloric acid, and two molecules of caustic soda.

Referring t0 the drawing, I provide a plurality of towers, preferably three, numbered respectively 5, 6 and 7. These towers are similar in construction to the so'called mover towers employed in the manufacture of sulfuric acid, being constructed of acidproof material and packed with vitrified or stoneware bricks or balls. The towers 5, 6 and 7 are connected by acid-proof pipes 8 and 9 adapted to carry gases and vapors from the upper portion of each tower to the lower portion of the succeeding tower. A pipe 10 connects the upper portion of the tower 7 to the first of a series of tourills or receivers 11 such as are commonly employed in the manufacture of hydrochloric acid. The tourills 11 are connected by pipes 12 which permit the passage of gases serially therethrough. The last tourill 11 of the series is connected by a pipe 14 to the lower portion of a tower 15 similar to those prea pump to the upper portion of the-tower 7 andviously described and having an outlet pipe 16 connected to a blower 17 which serves to draw the gases and vapors through the system.

lVater is delivered to the upper portion of the tower 15 by a pipe 18 and passes downwardly in contact with the gases and vapors rising through the tower, finally collecting in the receiving portion 19 of the tower after having absorbed the hydrochloric acid present in the gases and vapors. From the receiving portion 19 the saturated solution of acid Hows through api e 20 to the adjacent tourill 11 and thence t rough pipes 21 and preceding tourills 11. From the first tourill 11 of the series the acid is delivered by a pipe 22 -to the sump 23. The acid collected inthe tourill 11 adjacent the tower 15 is a substantially pure solution of hydrochloric acid gas and aportioii is withdrawn through the pipe 24 to the carboy 25.

The liquid collected in the sump -23 con.- sists of a water solution of hydrochloric acid gas containing some sulfuric acid and has a gravity of about 23 Baume. It is raised by 27 and delivered through a pipe 28 passes 4downwardly therein in contact with the gases and vapors rising therethrough lpassing into the receiving portion 29 of the towel' and thence through a pipe 30 into the sump 31. The liquid thus collected consists of a water solution of hydrochloric acid gas containing a higher proportion of sulfuric acid and has a. gravity of about'36 Baume.

The liquid is lifted by a pump 3Q and delivered by a pipe 33 to the upper portion of thetower 6 and passes downwardly therethrough in contact with the gases rising therein. The liquid accumulates in the receiving portion 34 of the tower and is delivered through a pipe 35 to the sump 36.

' The liquid thus collected is sulfuric acid carrying a relatively small proportion ofhydiochloric acid gas and water and has a gravity of about 50 Baume.

The acid from the sump 36 is lifted by the pump 37 and is delivered through the treated in a concentrator 43 until the gravity is increased to 65.5 or 66 Baume.

`Sulfur dioXidis produced in the burner and is delivered tothe lower portion of the tower 5 through a pipe 45, passes upwardly in the tower 5 where its temperature is utilized in distilling off water and any hydrochloric acid which may be present. The mixed sulfur dioxid and hydrochloric acid gas and water vapor passthrough the pipe 8 to the lower portion of the tower 6 Y where they are mixed with chlorin, delivered to thel lower portion of the tower 6 through a pipe 46 from a series of electrolytic cells 47 in whicha solution of common salt or sodium chlorid is subjected to the action of electric current from a source of power 4S. The mixture of sulfur dioxid and chloriii in the presence of water reacts to produce sulfuric and hydrochloric acids. The sulfuric acid passes downwardly with the liquid descending in the tower while the greater portion of the hydrochloric acid, together with some sulfur dioxid and chlorin,

pass through the pipe 9 into the tower 7 where the reaction is completed and from which hydrochloric acid gas carrying a relatively small proportion of sulfuric acid is delivered through the pipe 10 'to the tourills 11 as previously described.

The solution of caustic lye or sodium hydrate which is a. by-product of the electrolysis in the cells 47 is conveyed by a pipe 49 to an evaporator 50 from which caustic soda is recovered.

lVhile I have described iny process more particularly with reference to hydrochloric acid it is to be understood that other halogens may be substituted for chlorin with the resulting formation ofcorresponding haloid j acids.

From the foregoing it will be readily understood that I have perfected a continuous process of producing sulfuric and haloid acids and incidentall sodium'hydrate, thus accomplishing a resu t which has heretofore required at least two distinct processes, and that, through the operation of my rocess, I am able to recover all of the material used in a desirable and useful form and without the necessity of resortin to subsidiary rocesses to convert and uti ize the byro ucts. By following my process it is possi le to recover from the same materials heretofore utilized in producinr hydrochloric acid dstroyed in the hydrochloric acid process as heretofore practised, and sodium hydrate in place of the useless sodium sulfate which forms a large proportion of the product of the common hydrochloric acid process. .My process as herein described is exceedingly simple, requiring no apparatus in addition to that normally employed in producing sulfuric and hydrochloric acidlsother than the chlorin cells, which are of a common type well understood and exceedingly eiiicient.

I am enabled to eliminate the salt cake fure nace employed in the usual hydrochloric acid process and requiring the arduous labor of numerous attendants.' Various cha es may be made in the process as hereinbe ore described including variation of the apparatus employed and the regulation thereof without departing from the spirit and scope of the inventionY or sacrificing an of its material advantages, the form hereinbefore described being merely the preferred embodiment hereof.

I claim:

1. A process of producing sulfuric and haloid acids which comprises successively introducing and concurrently combining sulfur dioxid and a halogen in a flowing stream consisting of a mixture of saidacids with water, said stream bein finally subjected to the actionuof sulfur dioxid alone to separate the haloid acid therefrom.

. 2. A process of producing sulfuric and haloid acids which comprises successively introducing and concurrently combining sulfurdioxid and a halogen in a flowing stream of said acids containing water',=the sulfuric acid presentin said stream being pro ressively concentrated durin its travel, sai stream being finally Subject'e to the action of sulfur dioxid alone to 'separate the haloid acid therefrom.

3. A process of producing sulfuric and haloid acids which comprises successively introducing and concurrently combining sulfur dioxid and a halogen in' a flowing stream of said acids, concentrating the sulfuric acid progressively, subjecting the stream finally tothe action of sulfur dioxid alone to separateJ the haloid acid therefrom,"

alone both sulfuric acid, which is normally Itinuously, introducin and absorbing the aseous haloid acid in water to form the had acid portion of said stream.

4:. A process of producing sulfuric and haloid acids which comprises introducing and concurrently'combining sulfur dioxi and a halogen in a flowing vstream of said acids,y progressively concentrating the sulfuric acid, separating the gaseous haloid acid therefrom, absorbing the aseous haloid acid in water to form the ha oid acid portion of said stream `and withdrawing some of the haloid acid solution from said stream.

5. A process of producing sulfuric -and haloid acids which comprises introducin and concurrently combining sulfur dioxid and a halogen in a flowing stream -of said acids, continuously replenishing said stream with water, absorbing haloid acid gas in said water, recovering a ortion of the solution of haloid acid, an absorbing haloid acid gas mixed with vapors of sulfuric acid in the remainderof said solution to form said stream.

6. A process of .producing sulfuric and haloid acids which comprises introducing hot sulfur dioxid to a flowing stream of said acids containing water to distil out the haloid acid and a portion of the Water, conveying the mixture of sulfur dioxid, haloid acid gas and water vapor to another portion of said stream, 'introducing a halogen to said stream and concurrently combining the sulfur dioxid, halogen and water.

7.k A process of producing sulfuric and haloid acids which -comprises introduc' hot sulfur dioxid into a flowing streamuil said acids containingl water to distil out the haloid acid gas, conveying the mixture of sulfur dioxid and haloid acid and water vapor to another portion of said stream, in-

troducing a halogen to. said stream, concur- `conveying the escaping gases to still another portion .of said stream to complete the reioo action and to wash the gaseous haloid acid. Y

8. A process of producing sulfuric and haloid acids which comprises establishing a body of said ,acids containing water, introduc' and concurrentlyV combining sulfur dioxid and a halogen with said water, separatingthe haloid acid in a seous condition as formed, absorbing t e gaseous haloid acid in water, withdrawin a portion of the solution thus formed, an utilizin a portion of the 'solution to establish said body of sulfuric and haloid acids.-

9. A process ofproducing-sulfuric and haloid acids which comprises causing a-I stream of said acidsand water to flow conand concurrentl combiningsulfur dioxid and a halogen with7 the solution thus formed and said water, separating the haloid acid in a gaseous condition as formed, absorbing the recovering a portion of the solution thus formed and utilizing the remainder to form said stream. 11. A process of producing sulfuric and haloid acids which comprises successivelyl introducing and concurrently combining sulfur dioxid and a halogen with water,

causing the stream of water and acids to flow in one direction, nally subjecting said stream to the action of sulfur diox'd alone and separating and causing the gaseous lialoid acid to flow in the Opposite direction.

12. A process of producing s'ulfuricand` i haloid acids which comprises establishing a flowing stream of said acids with water,

establishing a counter current of gases by successively introducing sulfur dioxid and a halogen to said stream and concurrently combining said sulfur dioxid and halogen y with said water.

13. A process of producing sulfuric and hulod acids which comprises establishing a .flowing stream'of said acids with water, establishing a counter current of 'gases 'by successively introducing sulfur dioxid and a halogen to said stream, concurrently combining said sulfur dioxid and halogen with said Water, separating the gaseous haloid acid as formed, and conveying' it in the direction of said counter wrront.

14. A4 recess of producing sulfuric and haloi-d which comprises establishing' a flowing stream of said acids with water, es-

tablishing a counter current ofgases including sulfur dioxid `and .a'fhalogem concurrently combining said sulfur dioxid and' halogen with :said water, separating the gaseoushaloid acid as formed,` conveying it inthe direction ofssid'ooimter current, ab-v sorbing said haloid acid in Water, recovering a .portion or the' solution and delivering the remainder to said stream. -l Iii-testimony whereof 1I aiix my signature.

rimini 'roer-ER.. 

